Thiol-Lactam Initiated Radical Polymerization (TLIRP): Scope and Application for the Surface Functionalization of Nanoparticles

: Controlled polymerization techniques make possible fabrication of polymers with desired molecular weights, narrow dispersity, and also tailor-making of advanced hybrid materials. Thiol-Lactam Initiated Radical Polymerization (TLIRP) was introduced in 2002 and developed during the last two decades. The thiol/lactam combination enables one to generate radicals that can initiate the polymerization of vinyl-based monomers. The study of the mechanism and kinetics of TLIRP revealed the characteristics of living polymerization for TLIRP. Moreover, TLIRP has been used successfully for the synthesis of homopolymers, block copolymers, and statistical copolymers with polydispersity below 2.0. Especially, TLIRP provides a very straightforward method for grafting polymer brushes on the surface of nanoparticles. We review herein the systems developed for TLIRP and their applications for macromolecular engineering, with an emphasis on the surface functionalization of nanoparticles via the grafting-from approach.

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Synthesis of Poly(ester-graft-methyl methacrylate) on a Macroinitiator with Lateral Sulfonyl Chloride Groups by Atom Transfer Radical Polymerization

Polymer Science Series B ◽

10.1134/s1560090421040072 ◽

2021 ◽

Vol 63 (4) ◽

pp. 385-391

Author(s):

T. K. Meleshko ◽

A. B. Razina ◽

N. N. Bogorad ◽

M. P. Kurlykin ◽

A. V. Kashina ◽

...

Keyword(s):

Mechanical Properties ◽

Methyl Methacrylate ◽

Atom Transfer Radical Polymerization ◽

Radical Polymerization ◽

Polymer Brushes ◽

Sulfonyl Chloride ◽

Physical And Mechanical Properties ◽

Degree Of Polymerization ◽

Side Chains ◽

Grafting From

Abstract New polymer brushes with an ester backbone and poly(methyl methacrylate) side chains are synthesized by polycondensation and polymerization methods. The initiating groups are sulfonyl chloride groups laterally attached to the polyester chain. PMMA side chains are grafted by the ATRP method according to the “grafting from” multicenter macroinitiator strategy. The conditions for the polymerization processes in a controlled mode are selected, and the ways of targeted regulation of the degree of polymerization of methacrylate side chains are determined. Using the synthesized copolymers self-supporting films are obtained, and their physical and mechanical properties are studied.

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Mechanism and kinetics of the imidazolidinone nitroxide-mediated free-radical polymerization of styrene

Journal of Polymer Science Part A Polymer Chemistry ◽

10.1002/pola.10582 ◽

2002 ◽

Vol 41 (2) ◽

pp. 327-334 ◽

Cited By ~ 15

Author(s):

Paul Dervan ◽

Fawaz Aldabbagh ◽

Per B. Zetterlund ◽

Bunichiro Yamada

Keyword(s):

Free Radical ◽

Radical Polymerization ◽

Free Radical Polymerization ◽

Mechanism And Kinetics ◽

Kinetics Of

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Mechanism and kinetics of the radical polymerization of acrylamide in inverse micelles

Makromolekulare Chemie Macromolecular Symposia ◽

10.1002/masy.19900310106 ◽

1990 ◽

Vol 31 (1) ◽

pp. 27-40 ◽

Cited By ~ 3

Author(s):

Françoise Candau

Keyword(s):

Radical Polymerization ◽

Inverse Micelles ◽

Mechanism And Kinetics ◽

Kinetics Of

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Facile Synthesis of Hydrophilic Homo-Polyacrylamides via Cu(0)-Mediated Reversible Deactivation Radical Polymerization

Polymers ◽

10.3390/polym13121947 ◽

2021 ◽

Vol 13 (12) ◽

pp. 1947

Author(s):

Fehaid M. Alsubaie ◽

Othman Y. Alothman ◽

Basheer A. Alshammari ◽

Hassan Fouad

Keyword(s):

Radical Polymerization ◽

Water Soluble ◽

Side Reactions ◽

Controlled Polymerization ◽

Molecular Weights ◽

Linear Evolution ◽

Copper Bromide ◽

Reversible Deactivation ◽

Reversible Deactivation Radical Polymerization ◽

Experimental Number

In this work, copper-mediated reversible deactivation radical polymerization (RDRP) of homo-polyacrylamides was conducted in aqueous solutions at 0.0 °C. Various degrees of polymerization (DP = 20, 40, 60, and 80) of well-defined water-soluble homopolymers were targeted. In the absence of any significant undesirable side reactions, the dispersity of polydiethylacrylamide (PDEA) and polydimethylacrylamide (PDMA) was narrow under controlled polymerization conditions. To accelerate the polymerization rate, disproportionation of copper bromide in the presence of a suitable ligand was performed prior to polymerization. Full conversion of the monomer was confirmed by nuclear magnetic resonance (NMR) analysis. Additionally, the linear evolution of the polymeric chains was established by narrow molecular weight distributions (MWDs). The values of theoretical and experimental number average molecular weights (Mn) were calculated, revealing a good matching and robustness of the system. The effect of decreasing the reaction temperature on the rate of polymerization was also investigated. At temperatures lower than 0.0 °C, the controlled polymerization and the rate of the process were not affected.

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